1. Field of the Invention
This invention relates to a coating composition, a process for producing optical elements having excellent durability as well as good film hardness, scratch resistance and adhesion using the coating composition; and to optical elements produced by the process.
2. Description of the Related Art
Various methods have been proposed for improving the scratch resistance of plastic lenses which include coating plastic lenses with a coating composition made of an organosilicon compound as the major raw material, followed by curing the lenses to form a cured film thereon. The scratch resistance of plastic lenses is generally improved by employing a technique of increasing the content of inorganic oxide fine particles in the coating composition.
For example, Japanese Laid-Open Patent Application No. 10640/1988 discloses an optical element comprising a cured film made of a coating composition applied to a plastic lens substrate, the coating composition for which contains high-concentration colloidal silica, a type of fine inorganic particles, and a trifunctional organic compound. The high-concentration colloidal silica accounts for from 70 to 95 mole % (in terms of its solids content) based on the total amount of the composition.
However, the optical element disclosed in the above-cited patent, which has a cured film containing high-concentration inorganic fine particles, is problematic in that the stresses generated by the substrate and the high-concentration inorganic fine particles-containing cured film are liable to lower the adhesion between the cured film and the antireflection film formed thereon.
Methods of adding high-concentration inorganic fine particles to the coating film or increasing the degree of crosslinking in the film are generally employed for hardening the coating film. Anyhow, when the coating film is hardened, the hard film does not absorb the stress change resulting from the antireflection film formed thereon, and the interface between the hard film and the antireflection film is distorted, thereby lowering significantly the adhesion between the two films.
This invention provides a coating composition capable of forming a cured film having excellent scratch resistance and excellent adhesion between the cured film and an antireflection film formed thereon, an optical element having excellent scratch resistance, whose adhesion between the cured film and the antireflection film is little impaired, and a process for producing such optical elements.
In accordance with the invention, a coating composition for a cured film to be formed between a plastic substrate and an antireflection film made of an inorganic oxide contains an organosilicon compound and an adhesion improver made of an acetylene compound having a specific structure as described below.
Specifically, the invention provides a coating composition for forming a cured film between a plastic substrate and an antireflection film made of an inorganic oxide, which contains an organosilicon compound and an adhesion improver made of an acetylene compound of the general formulas (I-a) to (I-d): 
wherein Ra and Rc each independently represent a hydrogen atom or an optionally branched alkyl group having from 1 to 5 carbon atoms; Rb and Rd each independently represent an optionally branched alkyl group having from 2 to 8 carbon atoms; Re and Rf each independently represent an optionally branched alkyl group having from 1 to 3 carbon atoms; m and n each indicate an integer of 1 or more; and mxe2x80x2 and nxe2x80x2 each indicate an integer of 0 or more;
The invention also includes a process for producing optical elements, which comprises forming a cured film of the coating composition described herein on a plastic substrate, and forming an antireflection film of an inorganic oxide on the cured film, as well as an optical element having a cured film made of the coating composition formed on a plastic substrate, and having an antireflection film made of an inorganic oxide formed on the cured film, which may be produced by this process.
The coating composition of the invention contains an acetylene glycol compound of formula (I-a) or (I-b), or an acetylene compound of formula (I-c) or (I-d), and the adhesion between its cured film and the antireflection film that overlies it is good for a long time even when the cured film contains high-concentration inorganic fine particles. When the antireflection film contains a metal atom but not a metal oxide, the affinity between the metal atom and the triple bond in the acetylene glycol compound of formula (I-a) or (I-b), a type of acetylene compounds, or that in the acetylene compound of formula (I-c) or (I-d), is better and the metal atom itself relaxes the stress of the antireflection film. In this case, therefore, the adhesion between the cured film and the antireflection film is higher.
In formulas (I-a) and (I-b), Ra and Rc each represents a hydrogen atom or an optionally branched alkyl group. For these, preferred is a linear or branched alkyl group having from 1 to 5 carbon atoms, including, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and pentyl groups. For Rb and Rd each representing an optionally branched alkyl group, preferred is a linear or branched alkyl group having from 2 to 8 carbon atoms, including, for example, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and pentyl groups. m and n independently are integers of 1 or more, and preferably from 4 to 12.
The acetylene glycol compound of formula (I-a) is, for example, 2,4,7,9-tetramethyl-5-decyne-4,7-diol. The acetylene glycol compound of formula (II) is, for example, an adduct of 2,4,7,9-tetramethyl-5-decyne-4,7-diol having from 3 to 10 moles of polyoxyethylene added thereto.
The acetylene compounds of formulas (I-a) and (I-b) are known and are disclosed in, for example, Japanese Laid-Open Patent Application Nos. 53570/1984, 161473/1985, 99217/1988, 63288/1991, 163038/1991, 188087/1995, 265690/1998 and 20104/1999; International Patent Publication No. 503050/2000; Japanese Laid-Open Patent Application Nos. 43601/1996, 43602/1996, 43603/1996 and 43604/1996. However, the applications of the compounds disclosed in these documents are as surfactants for improving the defoaming property of the compositions containing the compound and for improving the dispersibility and the wettability of a dye in the compositions, without any suggestions of the use of these acetylene glycol compounds for improving the long-lasting adhesion to an antireflection film of a cured film even though it contains high-concentration inorganic fine particles, as in this invention.
The content of the acetylene glycol compound of formula (I-a) or (I-b) in the coating composition preferably ranges from 1 to 5% by weight based on the total weight of the composition.
The acetylene compounds of formulas (I-c) or (I-d) are novel compounds that are obtained starting from the acetylene glycol compounds of formulas (I-a) or (I-b). For producing them, the hydroxyl group that is present at the xcex1-position relative to the triple bond in formula (I-a), or the terminal hydroxyl group of the polyethylene glycol that is presented at the xcex1-position relative to the triple bond in formula (I-b), is reacted. The solvent to be used for the reaction is methylene chloride. Using 2.2 equivalents of tosyl chloride, 3 equivalents of triethylamine and 0.1 equivalents of dimethylaminopyridine, the starting compound is tosylated, and then 2.2 equivalents of an alkyne compound such as methylacetylene (propyne) is added thereto and reacted to obtain the intended compound. The reaction solvent to be used may be anhydrous THF.
In formulas (I-c) and (I-d), Ra and Rc each represents a hydrogen atom or an optionally branched alkyl group. For these, preferred is a linear or branched alkyl group having from 1 to 5 carbon atoms, including, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and pentyl groups. For Rb and Rd each representing an optionally branched alkyl group, preferred is a linear or branched alkyl group having from 2 to 8 carbon atoms, including, for example, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and pentyl groups. Re and Rf each represents an optionally branched alkyl group having from 1 to 3 carbon atoms m and n each are an integer of 1 or more, and preferably from 4 to 12. mxe2x80x2 and nxe2x80x2 each are integers of 0 or more, and preferably from 0 to 2.
The content of the acetylene compound of formula (I-c) or (I-d) in the coating composition preferably ranges from 1 to 5% by weight based on the total weight of the composition.
In the coating composition of the invention, the organosilicon compound is preferably at least one member selected from the group consisting of compounds represented by the following general formulas (II) and (III), and hydrolyzates thereof:
(R1)a(R3)bSi(OR2)4xe2x88x92(a+b)xe2x80x83xe2x80x83(II)
(X1O)3xe2x88x92x(R4)xSixe2x80x94Yxe2x80x94Si (R5)y(OX2)3xe2x88x92yxe2x80x83xe2x80x83(III)
wherein R1 and R3 each independently represent a monovalent hydrocarbon group having from 1 to 10 carbon atoms and having or not having a functional group; R2 represents an alkyl group having from 1 to 8 carbon atoms, an aryl group having from 6 to 10 carbon atoms, an aralkyl group having from 7 to 11 carbon atoms, or an acyl group having from 1 to 8 carbon atoms; a and b are each 0 or 1; and OR2""s may be the same or different; R4 and R5 each independently represents a monovalent hydrocarbon group having from 1 to 5 carbon atoms and having or not having a functional group; X1 and X2 each independently represents an alkyl group having from 1 to 4 carbon atoms or an acyl group having from 1 to 4 carbon atoms; Y represents a divalent hydrocarbon group having from 1 to 20 carbon atoms; x and y are each 0 or 1; X1""s may be the same or different; and X2""s may be the same or different).
In general formula (II), the monovalent hydrocarbon group having from 1 to 10 carbon atoms for R1 and R3 may include an alkyl group having from 1 to 10 carbon atoms, an alkenyl group having from 2 to 10 carbon atoms, an aryl group having from 6 to 10 carbon atoms, or an aralkyl group having from 7 to 11 carbon atoms. The alkyl and alkenyl groups may be linear, branched or cyclic. Examples of the alkyl group having from 1 to 10 carbon atoms are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, cyclopentyl and cyclohexyl groups. Examples of the alkenyl group having from 2 to 10 carbon atoms are vinyl, allyl, butenyl, hexenyl and octenyl groups. Examples of the aryl group having from 6 to 10 carbon atoms are phenyl, tolyl, xylyl and naphthyl groups. Examples of the aralkyl group having from 7 to 11 carbon atoms are benzyl, phenethyl and naphthylmethyl groups. These hydrocarbon groups may have a functional group introduced thereinto. The functional group includes, for example, a halogen atom, a glycidoxy group, an epoxy group, an amino group, a cyano group, a mercapto group, and a (meth)acryloxy group.
Examples of the monovalent hydrocarbon group having from 1 to 10 carbon atoms and having such a functional group are glycidoxymethyl, xcex1-glycidoxyethyl, xcex2-glycidoxyethyl, xcex1-glycidoxypropyl, xcex2-glycidoxypropyl, xcex3-glycidoxypropyl, (xcex1-glycidoxybutyl, xcex2-glycidoxybutyl, xcex3-glycidoxybutyl, xcex4-glycidoxybutyl, (3,4-epoxycyclohexyl)methyl, xcex2-(3,4-epoxycyclohexyl)ethyl, xcex3-(3,4-epoxycyclohexyl)propyl, xcex4-(3,4-epoxycyclohexyl)butyl, chloromethyl, xcex3-chloropropyl, 3,3,3-trifluoropropyl, xcex3-methacryloxypropyl, xcex3-acryloxypropyl, xcex3-mercaptopropyl, xcex2-cyanoethyl, N-(xcex2-aminoethyl)xcex3-aminopropyl and xcex3-aminopropyl groups.
On the other hand, the alkyl group having from 1 to 8 carbon atoms for R2 may be linear, branched or cyclic. Its examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopentyl and cyclohexyl groups. Examples of the aryl group having from 6 to 10 carbon atoms are phenyl, tolyl and xylyl groups; and examples of the aralkyl group having from 7 to 11 carbon atoms are benzyl and phenethyl groups. Examples of the acyl group having from 1 to 8 carbon atoms are an acetyl group.
Examples of the compounds represented by the general formula (II) are methyl silicate, ethyl silicate, n-propyl silicate, isopropyl silicate, n-butyl silicate, sec-butyl silicate, tert-butyl silicate, tetraacetoxysilane, methyltrimethoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltriamyloxysilane, methyltriphenoxysulane, methyltribenzyloxysilane, methyltriphenethyloxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyltrimethoxysilane, xcex1-glycidoxyethyltrimethoxysilane, xcex1-glycidoxyethyltriethoxysilane, xcex2-glycidoxyethyltriethoxysilane, xcex1-glycidoxypropyltrimethoxysilane, xcex1-glycidoxypropyltriethoxysilane, xcex2-glycidoxypropyltrimethoxysilane, xcex2-glycidoxypropyltriethoxysilane, xcex3-glycidoxypropyltrimethoxysilane, xcex3-glycidoxypropyltriethoxysilane, xcex3-glycidoxypropyltripropoxysilane, xcex3-glycidoxypropyltriphenoxysilane, xcex1-glycidoxybutyltrimethoxysilane, xcex1-glycidoxybutyltriethoxysilane, xcex2-glycidoxybutyltrimethoxysilane, xcex2-glycidoxybutyltriethoxysilane, xcex3-glycidoxybutyltrimethoxysilane, xcex3-glycidoxybutyltriethoxysilane, xcex4-glycidoxybutyltrimethoxysilane, xcex4-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, xcex2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, xcex2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, xcex2-(3,4-epoxycyclohexyl)ethyltripropoxysilane, xcex2-(3,4-epoxycyclohexyl)ethyltributoxysilane, xcex2-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, xcex3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, xcex3-(3,4-epoxycyclohexyl)propyltriethoxysilane, xcex4-(3,4-epoxycyclohexyl)butyltrimethoxysilane, xcex4-(3,4-epoxycyclohexyl)butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, xcex1-glycidoxyethlmethyldimethoxysilane, xcex1-glycidoxyethylmethyldiethoxysilane, xcex2-glycidoxyethylmethyldimethoxysilane, xcex2-glycidoxyethylmethyldiethoxysilane, xcex1-glycidoxypropylmethyldimethoxysilane, xcex1-glycidoxypropylmethyldiethoxysilane, xcex2-glycidoxypropylmethyldimethoxysilane, xcex1-glycidoxypropylmethyldiethoxysilane, xcex3-glycidoxypropylmethyldimethoxysilane, xcex3-glycidoxypropylmethyldiethoxysilane, xcex3-glycidoxypropylmethyldipropoxysilane, xcex3-glycidoxypropylmethyldibutoxysilane, xcex3-glycidoxypropylmethyldiphenoxysilane, xcex3-glycidoxypropylethyldimethoxysilane, xcex3-glycidoxypropylethyldiethoxysilane, xcex3-glycidoxypropylvinyldimethoxysilane, xcex3-glycidoxypropylvinyldiethoxysilane, xcex3-glycidoxypropylphenyldimethoxysilane, xcex3-glycidoxypropylphenyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, xcex3-chloropropyltrimethoxysilane, xcex3-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, xcex3-methacryloxypropyltrimethoxysilane, xcex3-mercaptopropyltrimethoxysilane, xcex3-mercaptopropyltriethoxysilane, xcex2-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, N-(xcex2-aminoethyl)-xcex3-aminopropyltrimethoxysilane, N-(xcex2-aminoethyl)-xcex3-aminopropylmethyldimethoxysilane, xcex3-aminopropylmethyldimethoxysilane, N-(xcex2-aminoethyl)-xcex3-aminopropylmethyldiethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, xcex3-chloropropylmethyldiethoxysilane, xcex3-chloropropylmethyldimethoxysilane, dimethyldiacetoxysilane, xcex3-methacryloxypropylmethyldimethoxysilane, xcex3-methacryloxypropylmethyldiethoxysilane, xcex3-mercaptopropylmethyldimethoxysilane, xcex3-mercaptopropylmethyldiethoxysilane, methylvinyldimethoxysilane, and methylvinyldiethoxysilane.
On the other hand, in the general formula (III), the alkyl group having from 1 to 4 carbon atoms for X1 and X2 includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl groups; and the acyl group having from 1 to 4 carbon atoms is, for example, preferably an acetyl group. These X1 and X2 may be the same or different.
The monovalent hydrocarbon group having from 1 to 5 carbon atoms for R4 and R5 includes an alkyl group having from 1 to 5 carbon atoms and an alkenyl group having from 2 to 5 carbon atoms. These may be linear or branched. Examples of the alkyl group are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and pentyl groups. Examples of the alkenyl group are vinyl, allyl and butenyl groups. These hydrocarbon groups may have a functional group introduced thereinto. For the functional group and the functional group-having hydrocarbon group, referred to are the same as those mentioned hereinabove for R1 and R3 in the general formula (II). These R4 and R5 may be the same or different.
For the divalent hydrocarbon group having from 1 to 20 carbon atoms for Y, preferred are an alkylene group and an alkylidene group, including, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, ethylidene and propylidene groups.
In the above compounds, x and y are 0 or 1; the OX1""s may be the same or different and the OX2""s may also be the same or different.
Examples of the compounds represented by the general formula (III) are methylenebis(methyldimethoxysilane), ethylenebis(ethyldimethoxysilane), propylenebis(ethyldiethoxysilane), and butylenebis(methyldiethoxysilane).
In the coating composition of the invention, the organosilicon compound may be one or more compounds selected from the compounds represented by the general formulas (II) and (III) and their hydrolyzates. The hydrolyzates may be prepared by adding an aqueous basic solution such as an aqueous sodium hydroxide or ammonia solution or an aqueous acidic solution such as an aqueous hydrochloric acid solution to the compound represented by general formula (II) or (III), followed by stirring the mixture.
If desired, a curing agent as well as various organic solvents and surfactants for the purposes of improving wettability during the application and improving the smoothness of the cured film, UV absorbents, antioxidants, light stabilizers and anti-aging agents may be added as long as the properties of the coating composition itself and the cured film are not influenced.
Preferably, the coating composition of the invention further contains inorganic oxide fine particles. These inorganic oxide fine particles are not specifically defined, and may be arbitrarily selected from known ones. Examples of the inorganic oxide fine particles are fine particles of single metal oxides such as aluminum oxide, titanium oxide, antimony oxide, tin oxide, zirconium oxide, silicon oxide, cerium oxide, and iron oxide; as well as fine particles of composite oxides such as fine particles of a tin oxide-zirconium oxide-tungsten oxide composite as disclosed in Japanese Laid-Open Patent Application No. 25603/1994; fine particles of a tin oxide-tungsten oxide composite as disclosed in Japanese Laid-Open Patent Application No. 217230/199 1; fine particles of a composite metal oxide of titanium oxide, cerium oxide and silicon oxide as disclosed in Japanese Laid-Open Patent Application No. 113760/1996; fine particles of a titanium oxide-zirconium oxide-tin oxide composite as disclosed in Japanese Laid-Open Patent Application No. 306258/1998; and fine particles of a titanium oxide-zirconium oxide-silicon oxide composite and of a stannic oxide-zirconium oxide-tungsten oxide composite as disclosed in Japanese Laid-Open Patent Application No. 21901/1997.
The mean particle size of the inorganic oxide fine particles may be generally in the range of from 1 to 500 nm. One or more the same or different types of such inorganic oxide fine particles may be used either singly or in the form of a mixture. Though varying depending on the type of the plastic substrate, the constitution of the antireflection film, the composition of the cured film and the fabricating conditions, the cured film made of the coating composition that contains the acetylene glycol compound enjoys good adhesion to the antireflection film made of an inorganic oxide even when the content of the inorganic oxide fine particles in the coating composition is high as 30% by weight based on the total weight of the composition.
The preferred content of the inorganic oxide fine particles is from about 10 to about 30% by weight based on the total weight of the coating composition, though varying depending on the plastic substrate, the constitution of the antireflection film, the composition of the cured film and the fabricating conditions.
When the amount of the inorganic oxide fine particles is from 10 to 30% by weight of the coating composition prior to curing, the preferred content of the inorganic oxide fine particles to be in the cured film made of the coating composition of the invention is from 30 to 60% by weight based on the total weight of the coating composition, though varying depending on the plastic substrate, the constitution of the antireflection film, the composition of the cured film and the fabricating conditions.
In the invention, applying the coating composition onto the surface of a plastic lens substrate, employable is carried out by any ordinary method of dipping, spin coating, or spraying. In view of need for face accuracy, especially preferred is dipping or spin coating. After it is applied to a plastic substrate, the coating composition is cured by drying it in hot air or by exposing it to actinic energy rays. Preferably, the coating composition is cured in hot air at 70 to 200xc2x0 C., and more preferably at 90 to 150xc2x0 C. For the actinic energy rays, preferred are far-infrared rays not damaging the film by heat.
The inorganic oxide used to form the antireflection film in the invention is not specifically defined and may be any ordinary one generally known as the raw material for antireflection films, including, fore example, Ta2O5, Y2O3, ZrO2, SiO2, TiO2, Al2O3, and Nb2O5.
A base layer made of a metal or metal oxide film may be disposed between the antireflection film and the cured film made of the coating composition of the invention.
The plastic substrate is not specifically defined, and may include, for example, methyl methacrylate homopolymers, copolymers of methyl methacrylate with at least one other monomer, diethylene glycol bisallylcarbonate homopolymers, copolymers of diethylene glycol bisallylcarbonate with at least one other monomer, sulfur-containing copolymers, halogen-containing copolymers, polycarbonate, polystyrene, polyvinyl chloride, unsaturated polyesters, polyethylene terephthalate, polyurethane, and polythiourethane.
The invention will be described in more detail with reference to the following Examples, which, however, are not intended to restrict the scope of the invention.